JPH0344106B2 - - Google Patents
Info
- Publication number
- JPH0344106B2 JPH0344106B2 JP58009256A JP925683A JPH0344106B2 JP H0344106 B2 JPH0344106 B2 JP H0344106B2 JP 58009256 A JP58009256 A JP 58009256A JP 925683 A JP925683 A JP 925683A JP H0344106 B2 JPH0344106 B2 JP H0344106B2
- Authority
- JP
- Japan
- Prior art keywords
- polyphenylene ether
- flame
- ether resin
- resin composition
- flame retardant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000203 mixture Substances 0.000 claims description 56
- 229920001955 polyphenylene ether Polymers 0.000 claims description 51
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 30
- 239000003063 flame retardant Substances 0.000 claims description 30
- 239000011342 resin composition Substances 0.000 claims description 24
- 239000011347 resin Substances 0.000 claims description 14
- 229920005989 resin Polymers 0.000 claims description 14
- 239000004793 Polystyrene Substances 0.000 claims description 12
- 229920002223 polystyrene Polymers 0.000 claims description 12
- 150000002148 esters Chemical class 0.000 claims description 11
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- 229910052796 boron Inorganic materials 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- -1 polyphenylene Polymers 0.000 claims description 7
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 230000003110 anti-inflammatory effect Effects 0.000 claims description 4
- 239000003623 enhancer Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- GHMDTEDTNDZHTB-UHFFFAOYSA-N tris(2-phenylcyclohexyl) borate Chemical compound C1CCCC(C=2C=CC=CC=2)C1OB(OC1C(CCCC1)C=1C=CC=CC=1)OC1CCCCC1C1=CC=CC=C1 GHMDTEDTNDZHTB-UHFFFAOYSA-N 0.000 claims description 4
- YVVYMSXDQGDASK-UHFFFAOYSA-N 1,2,3-tribromo-4-[2-(2,3,4-tribromophenoxy)ethoxy]benzene Chemical compound BrC1=C(Br)C(Br)=CC=C1OCCOC1=CC=C(Br)C(Br)=C1Br YVVYMSXDQGDASK-UHFFFAOYSA-N 0.000 claims description 3
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical group [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 3
- 239000000945 filler Substances 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- 229920000265 Polyparaphenylene Polymers 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 150000005826 halohydrocarbons Chemical group 0.000 claims description 2
- WLLZFOKCJMRIQJ-UHFFFAOYSA-N 2,3-dimethyl-7-oxabicyclo[2.2.1]hepta-1,3,5-triene Chemical compound C1=C(O2)C(C)=C(C)C2=C1 WLLZFOKCJMRIQJ-UHFFFAOYSA-N 0.000 claims 1
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims 1
- 239000012779 reinforcing material Substances 0.000 claims 1
- 239000000654 additive Substances 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 239000004721 Polyphenylene oxide Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 229920006380 polyphenylene oxide Polymers 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 150000002894 organic compounds Chemical class 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 3
- 238000002845 discoloration Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
- KPTMGJRRIXXKKW-UHFFFAOYSA-N 2,3,5-trimethyl-7-oxabicyclo[2.2.1]hepta-1,3,5-triene Chemical compound O1C2=C(C)C(C)=C1C=C2C KPTMGJRRIXXKKW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004727 Noryl Substances 0.000 description 1
- 229920001207 Noryl Polymers 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229920003247 engineering thermoplastic Polymers 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000002557 mineral fiber Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000834 poly(ferrocenylene) polymer Polymers 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/55—Boron-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/02—Halogenated hydrocarbons
Description
【発明の詳細な説明】
ポリフエニレンエーテル樹脂組成物の如き重合
体に混入したとき、新規な耐燃性非変色ポリフエ
ニレンエーテル樹脂組成物を生成する新規な難燃
剤組成物または添加剤を提供する。難燃剤組成物
は250〜300℃で安定である硼素含有エステルおよ
び安定ハロゲン化有機化合物の組成物からなる。DETAILED DESCRIPTION OF THE INVENTION New flame retardant compositions or additives are provided which, when incorporated into polymers such as polyphenylene ether resin compositions, produce novel flame resistant, non-discoloring polyphenylene ether resin compositions. do. The flame retardant composition consists of a composition of a boron-containing ester and a stable halogenated organic compound that is stable at 250-300°C.
難燃剤組成物の製造法、および耐燃性ポリフエ
ニレンエーテル樹脂組成物、のみならず耐燃性ポ
リフエニレンエーテル樹脂組成物を成形する方法
および得られる成形品も含む。 It includes not only a method for producing a flame retardant composition and a flame-resistant polyphenylene ether resin composition, but also a method for molding the flame-resistant polyphenylene ether resin composition and the resulting molded article.
成形後の組成物は耐燃性であり、非変色である
成形品を提供する。 After molding, the composition is flame resistant and provides a molded article that is non-discoloring.
本発明は重合体、特にポリフエニレンオキサイ
ド（PPO）樹脂としても知られているポリフエ
ニレンエーテル樹脂を含有する組成物に、かかる
樹脂中に難燃剤組成物を混入したとき変色を防止
する新規な難燃性組成物または添加剤に関する。
本発明はまた少量ではあるが有効量の上記難燃剤
組成物およびポリフエニレンエーテル樹脂を含有
する耐燃性組成物にも関する。 The present invention provides novel methods for preventing discoloration in compositions containing polymers, particularly polyphenylene ether resins, also known as polyphenylene oxide (PPO) resins, when flame retardant compositions are incorporated into such resins. flame retardant compositions or additives.
The present invention also relates to flame resistant compositions containing small but effective amounts of the flame retardant compositions described above and polyphenylene ether resins.
広い観点において、難燃剤組成物は250〜300℃
で安定である硼素含有エステルおよび安定ハロゲ
ン化有機化合物の組合せまたは混合物からなる。
かかる難燃性組成物の好ましい具体例は約１〜約
３重量部の硼素含有エステルとの混合物の形での
約５〜約35重量部のハロゲン化有機化合物からな
り、ハロゲン化有機化合物は臭素化フエノキシア
ルカンである。好ましい耐燃性ポリフエニレンエ
ーテル樹脂組成物は、ポリ（２，６−ジアルキル
−１，４−フエニレン）エーテル樹脂例えばポリ
（２，６−ジメチル−１，４−フエニレン）エー
テル樹脂を含み組成物中に上記難燃剤組成物の有
効量を混入して作つた配合物からなる。ポリフエ
ニレンエーテル樹脂組成物に加える難燃性組成物
または添加剤を形成し、一緒にした硼素含有エス
テルおよび臭素化フエノキシアルカンの量は、ポ
リフエニレンエーテル樹脂組成物100重量部につ
いて難燃剤組成物約10〜約25重量部の範囲である
ことができる。 In broad terms, the flame retardant composition is 250-300℃
consisting of a combination or mixture of a boron-containing ester and a stable halogenated organic compound.
Preferred embodiments of such flame retardant compositions comprise from about 5 to about 35 parts by weight of a halogenated organic compound in a mixture with from about 1 to about 3 parts by weight of a boron-containing ester, wherein the halogenated organic compound comprises a bromine-containing ester. phenoxyalkanes. Preferred flame resistant polyphenylene ether resin compositions include a poly(2,6-dialkyl-1,4-phenylene) ether resin such as a poly(2,6-dimethyl-1,4-phenylene) ether resin in the composition. and an effective amount of the flame retardant composition described above. The amount of boron-containing ester and brominated phenoxyalkane combined to form a flame retardant composition or additive added to the polyphenylene ether resin composition is approximately 100 parts by weight of the polyphenylene ether resin composition. The fuel composition can range from about 10 to about 25 parts by weight.
本発明はまた難燃剤組成物を製造する方法、上
記組成物で耐燃性にされたポリフエニレンエーテ
ル樹脂組成物の製造法、耐燃性ポリフエニレンエ
ーテル樹脂組成物を成形する方法も含む、またそ
れから得られる耐燃性非変色成形品も含む。加工
後の組成物は耐燃性であるばかりでなく、成形時
に変色しない。 The present invention also includes a method of making a flame retardant composition, a method of making a polyphenylene ether resin composition made flame resistant with the composition, a method of molding a flame resistant polyphenylene ether resin composition, and It also includes flame-resistant, non-discoloring molded articles obtained therefrom. The composition after processing is not only flame resistant, but also does not discolor during molding.
ポリフエニレンエーテルは知られており、ヘイ
の米国特許第3306874号および第3306875号、およ
びスタマトフの米国特許第3257357号および第
3257358号（これらは引用してここに全て組入れ
る）を含む多くの刊行物に記載されている。高分
子量ポリフエニレンエーテルは比較的高い即ち
250℃以上の溶融粘度および軟化点を有する高性
能エンジニアリング熱可塑性樹脂であり、フイル
ム、繊維および成形品の形成を含む耐高温性を必
要とする多くの産業上の用途に有用である。 Polyphenylene ethers are known and are described in US Pat. Nos. 3,306,874 and 3,306,875 to Hay, and US Pat.
No. 3257358, all of which are incorporated herein by reference. High molecular weight polyphenylene ethers have relatively high i.e.
A high performance engineering thermoplastic with a melt viscosity and softening point above 250°C, useful in many industrial applications requiring high temperature resistance, including the formation of films, fibers and molded articles.
チツエクの米国特許第3383435号（これも引用
してここに組入れる）には、ゴム成分がブタジエ
ンの重合体および共重合体の如き不飽和型のもの
であるゴム変性スチレン樹脂−ポリフエニレンエ
ーテル樹脂を含むポリフエニレンエーテル−スチ
レン樹脂組成物が記載されている。スチレン樹脂
成分はポリフエニレンエーテルの成形性を改良す
る。 U.S. Pat. No. 3,383,435 (also incorporated herein by reference) to Chitsek discloses rubber-modified styrenic resin-polyphenylene ether resins in which the rubber component is of the unsaturated type, such as polymers and copolymers of butadiene. A polyphenylene ether-styrene resin composition is described. The styrene resin component improves the moldability of polyphenylene ether.
クツパー等の米国特許第3943191号、第3959211
号、第3974235号、第4101503号、第4101504号、
第4101505号、第4102850号および第4226761号に
は、難燃性添加剤を含む種々なポリフエニレンエ
ーテル樹脂組成物が記載されている。上記特許は
引用してここに組入れる。 U.S. Patents 3943191 and 3959211 to Kutzper et al.
No. 3974235, No. 4101503, No. 4101504,
Nos. 4,101,505, 4,102,850 and 4,226,761 describe various polyphenylene ether resin compositions containing flame retardant additives. The above patents are incorporated herein by reference.
ポリフエニレンエーテル組成物が成形時に変色
することなく耐燃性にすることができることをこ
こに見出した。これは、250〜300℃で安定である
硼素含有エステルおよび安定な臭素化フエノキシ
アルカンの組合せまたは混合物を含む難燃剤組成
物または添加剤によつて組成される。この組成物
の有効量をポリフエニレンエーテル組成物に混入
するとき、形成される組成物は耐燃性にされ、そ
れと同時に成形時に変色しない。 It has now been discovered that polyphenylene ether compositions can be made flame resistant without discoloration during molding. It is formulated with a flame retardant composition or additive that includes a combination or mixture of a boron-containing ester and a stable brominated phenoxyalkane that are stable at 250-300°C. When an effective amount of this composition is incorporated into a polyphenylene ether composition, the composition formed is rendered flame resistant while at the same time not discoloring upon molding.
臭素化フエノキシアルカンとしては例えば１，
２−ビス−（トリブロモフエノキシ）−エタンを使
用できる。 Examples of brominated phenoxyalkanes include 1,
2-bis-(tribromophenoxy)-ethane can be used.
硼素含有エステルの例にはトリ−（２−フエニ
ルシクロヘキシル）−ボレートがある。 An example of a boron-containing ester is tri-(2-phenylcyclohexyl)-borate.
難燃剤組成物を作るに当つては、一般に約１〜
約３重量部の硼素含有エステルおよび約５〜約35
重量部の臭素化フエノキシアルカンを一緒に混合
する。ポリフエニレンエーテル樹脂組成物を耐燃
性にするためには、ポリフエニレンエーテル樹脂
組成物100重量部について全難燃剤組成物約10〜
約25重量部を混入する、なお上記ポリフエニレン
エーテル樹脂組成物はポリブタジエン変性ポリス
チレンを含有することもでき、これはFG−834の
名でフオスター・グラントから入手できる。ポリ
フエニレンエーテルはまたスチレン樹脂との混合
物としても市場で入手しうる。米国特許第
3383435号および第3663654号参照。これらの混合
物は約25〜75％のポリスチレン単位を含有し、商
標名ノリル（NORYL）でゼネラル・エレクトリ
ツク・カンパニイから入手できる。 In preparing the flame retardant composition, generally about 1 to
about 3 parts by weight of a boron-containing ester and about 5 to about 35 parts by weight
Parts by weight of brominated phenoxyalkanes are mixed together. In order to make the polyphenylene ether resin composition flame resistant, the total flame retardant composition should be about 10 to 10 parts by weight for every 100 parts by weight of the polyphenylene ether resin composition.
The polyphenylene ether resin composition may also contain about 25 parts by weight of polybutadiene-modified polystyrene, which is available from Foster Grant under the name FG-834. Polyphenylene ethers are also commercially available as mixtures with styrene resins. US Patent No.
See Nos. 3383435 and 3663654. These mixtures contain about 25-75% polystyrene units and are available from General Electric Company under the trade name NORYL.
ポリフエニレンエーテル樹脂組成物の燃焼が生
ずる高温、400〜600℃で、臭素化フエノキシアル
カンおよび硼素含有エステルは相互反応してチヤ
ーを作り、炎を急速に消す中間体を形成する、か
くしてすぐれた加工色を維持する。少量ではある
が有効量の消炎増強剤例えばフエロセンおよびポ
リフエロセンは、低濃度で消炎性を増強するため
に加えることができる。 At high temperatures, 400-600°C, where combustion of the polyphenylene ether resin composition occurs, the brominated phenoxyalkanes and boron-containing esters interact to form an intermediate that creates a char and rapidly extinguishes the flame, thus Maintains excellent processing color. Small but effective amounts of anti-inflammatory enhancers such as ferrocenes and polyferrocenes can be added at low concentrations to enhance anti-inflammatory properties.
これらの消炎増強剤はポリフエニレンエーテル
樹脂組成物100重量部について約0.3〜約３重量部
の量で加えることができる。 These anti-inflammatory enhancers can be added in amounts of about 0.3 to about 3 parts by weight per 100 parts by weight of the polyphenylene ether resin composition.
好ましい例において、本発明により意図するポ
リフエニレンエーテルは式
（式中、Ｑ、Q′、Q″およびＱはそれぞれ独立
に水素、炭化水素基、ハロゲン原子とフエニル核
の間に少なくとも２個の炭素原子を有するハロ炭
化水素基、炭化水素オキシ基およびハロゲン原子
とフエニル核の間に少なくとも２個の炭素原子を
有するハロ炭化水素オキシ基からなる群から選択
し、更にQ′、Q″およびＱはハロゲンであるこ
とができる。ただしＱおよびQ′は三級炭素原子
を含有しないのが好ましい、ｎは単量体残基の合
計数を表わし、少なくとも50の整数である）の繰
返し構造単位を有する。上記式に相当するポリフ
エニレンエーテルは前記ヘイおよびスタマトフの
米国特許明細書に見出すことができる。 In a preferred example, the polyphenylene ether contemplated by the invention has the formula (In the formula, Q, Q', Q'' and Q are each independently hydrogen, a hydrocarbon group, a halohydrocarbon group having at least two carbon atoms between a halogen atom and a phenyl nucleus, a hydrocarbonoxy group, and a halogen selected from the group consisting of halohydrocarbonoxy groups having at least 2 carbon atoms between the atom and the phenyl nucleus, and further Q', Q'' and Q can be halogen, provided that Q and Q' are It preferably contains no class carbon atoms (n represents the total number of monomer residues and is an integer of at least 50) repeating structural units. Polyphenylene ethers corresponding to the above formula can be found in the Hay and Stamatov US patents.
ここに使用するときポリフエニレンエーテルな
る語は上記式によつて表わされる重合体の範囲に
含まれるもののみならず他の樹脂との混合によつ
て変性されたポリフエニレンエーテルを含むもの
とする。米国特許第3383435号にはポリスチレン
の多くの性質を向上させ、同時に溶融体を改良す
るための手段が記載されている。米国特許第
3383435号の発明は、ポリフエニレンエーテルお
よび変性ポリスチレンを含むポリスチレンがあら
ゆる割合で混合でき、これら両成分の何れの性質
よりも改良された多くの性質を有する混合物を生
ぜしめることを見出したことに基いている。上記
特許に記載されている如く、ポリフエニレンエー
テルと混合しうるポリスチレンは式
（式中Ｒは水素、低級アルキル基またはハロゲン
であり、Ｚはビニル基、水素、ハロゲンおよび低
級アルキル基からなる群から選択した一員であ
り、ｐは０または１〜５の整数である）を有する
単量体から誘導された重合体単位少なくとも25重
量％を有するものである。この特許の好ましい組
成物はポリスチレンまたはゴム変性ポリスチレン
と組合せたポリ（２，６−ジアルキル−１，４−
フエニレン）エーテルである。低級アルキル基は
１〜６個の炭素原子を含有する。 As used herein, the term polyphenylene ether is intended to include not only those included within the scope of the polymers represented by the above formula, but also polyphenylene ethers modified by mixing with other resins. US Pat. No. 3,383,435 describes a means to improve many properties of polystyrene and at the same time improve the melt. US Patent No.
The invention of No. 3,383,435 is based on the discovery that polyphenylene ethers and polystyrenes, including modified polystyrenes, can be mixed in any proportion to produce a mixture that has many properties that are improved over the properties of either of these components. It is based. As described in the above patent, polystyrene which can be mixed with polyphenylene ether has the formula (wherein R is hydrogen, a lower alkyl group, or a halogen, Z is a member selected from the group consisting of a vinyl group, hydrogen, a halogen, and a lower alkyl group, and p is 0 or an integer from 1 to 5). at least 25% by weight of polymer units derived from monomers having The preferred compositions of this patent are poly(2,6-dialkyl-1,4-
(phenylene) ether. Lower alkyl groups contain 1 to 6 carbon atoms.
一般に耐燃性ポリフエニレンエーテル組成物を
製造する方法は、ポリフエニレンエーテル組成物
と難燃剤組成物を均質混合し、次いで各成分を配
合することを含む。好ましくは臭素化フエノキシ
アルカンと硼素含有エステルの組合せおよびポリ
フエニレンエーテルを先ず均質混合して予備混合
物を形成し、予備混合物を約500〜約600〓の高温
で配合用押出機に通す。押し出し配合物をペレツ
トにし、次いで例えばニユーベリー射出成形機で
所望の形に成形する。 Generally, a method for manufacturing a flame-resistant polyphenylene ether composition includes homogeneously mixing the polyphenylene ether composition and the flame retardant composition, and then blending each component. Preferably, the combination of brominated phenoxyalkane and boron-containing ester and polyphenylene ether are first intimately mixed to form a premix, and the premix is passed through a compounding extruder at an elevated temperature of about 500 to about 600 °C. The extrusion compound is pelletized and then molded into the desired shape, for example, in a Newberry injection molding machine.
本発明の難燃剤組成物は、ポリフエニレンエー
テルが従来使用されていたあらゆる目的、例えば
フイルム、繊維、成形品等に有用である。 The flame retardant compositions of the present invention are useful for all purposes for which polyphenylene ethers have traditionally been used, such as films, fibers, molded articles, and the like.
難燃剤組成物は、ポリフエニレンエーテル自体
と、またはそれと他の添加剤との組合せ、例えば
ポリスチレンおよびゴム変性ポリスチレンとの組
合せに使用して有利であり、特にかかる組成物の
加工および応用が、変色を生ぜしめたり、衝撃強
さが低下する高温の使用を必要とする加工および
用途に使用して有利である。 The flame retardant compositions are advantageous for use with polyphenylene ethers themselves or in combination with other additives, such as polystyrene and rubber-modified polystyrene, in particular the processing and application of such compositions. It is advantageous for use in processing and applications that require the use of high temperatures that can cause discoloration or reduce impact strength.
本発明の種類の組成物はまた一定の他の化学的
および物理的性質を改良するため従来より普通に
使用されている非樹脂系の補助成分も含有する。
非樹脂系補助剤には充填剤および／または強化
剤、例えば鉱物繊維（例えばクレー、タルク、硫
酸カルシウム等）、強化繊維（例えばガラス繊維、
グラフアイトホイスカー等）、酸化防止剤、染料、
顔料、可塑剤等を含む。これらは一般に全組成物
重量を基にして、１〜50％の範囲の少量ではある
が有効量加える。 Compositions of the type of the present invention also contain non-resin based adjunctive ingredients commonly used in the art to improve certain other chemical and physical properties.
Non-resin based adjuvants include fillers and/or reinforcing agents, such as mineral fibers (e.g. clay, talc, calcium sulfate, etc.), reinforcing fibers (e.g. glass fibers,
graphite whiskers, etc.), antioxidants, dyes,
Contains pigments, plasticizers, etc. These are generally added in small but effective amounts ranging from 1 to 50%, based on the total composition weight.
下記実施例は更に本発明を示すものであり、本
発明を限定するものと考えるべきでない。 The following examples further illustrate the invention and should not be considered as limiting the invention.
実施例 １
難燃剤組成物の組成および難燃剤組成物とポリ
フエニレンエーテルの配合物の組成および耐燃性
ポリフエニレンエーテルの性質を下表に示す。Example 1 The composition of the flame retardant composition and the blend of the flame retardant composition and polyphenylene ether and the properties of the flame resistant polyphenylene ether are shown in the table below.
表中、PPOは30℃でクロロホルム中で測定し
て、約0.5dl／ｇの固有粘度を有するポリ（２，
６−ジメチル−１，４−フエニレン）オキサイド
またはエーテルおよび耐衝撃ポリブタジエン変性
ポリスチレンを意味する。UL94およびSE は
アンダーライターズ・ラボラトリーズ・ブレチン
No.49の耐燃試験および基準を表わし、SEは自己
消化性の略記号であり、ローマ数字はULの格付
を示す。 In the table, PPO is poly(2,
6-dimethyl-1,4-phenylene) oxide or ether and impact-resistant polybutadiene-modified polystyrene. UL94 and SE are Underwriters Laboratories Bulletin
No. 49 Flame Resistance Test and Standard, SE stands for self-extinguishing and Roman numerals indicate UL rating.
PPOおよびポリスチレンは予備混合し、次い
でそれを１，２−ビス−（トリブロモフエノキシ）
−エタンおよびトリ−（２−フエニルシクロヘキ
シル）−ボレートの難燃剤組成物および消炎増強
剤フエロセンと混合した。配合物を混合し、450
〓の温度で押出機で押し出した。押し出したペレ
ツトを射出成形機で標準試験棒に550〓で成形し
た。 PPO and polystyrene are premixed and then mixed with 1,2-bis-(tribromophenoxy)
A flame retardant composition of -ethane and tri-(2-phenylcyclohexyl)-borate and the flame-retardant enhancer ferrocene were mixed. Mix the formulation, 450
It was extruded using an extruder at a temperature of 〓. The extruded pellets were molded into standard test bars using an injection molding machine at 550 mm.
表 実施例
１
PPO（登録商標） 25
耐衝撃ポリスチレン 75
１，２−ビス−（トリブロモフエノキシ）−エタン
15.2
トリ−（２−フエニルシクロヘキシル）−ボレート
3.0
フエロセン 0.7性 質
UL94試験 SE
加熱撓み温度、〓／264psi2″スパン 195
色 本来の非常に明るいもの
ノツチ付アイゾツト衝撃強さ 2.8
引張り降伏強さ 6600
極限引張り強さ 6100
伸び率、％ 53
上記結果から本発明による難燃剤組成物がポリ
フエニレンエーテル組成物を耐燃性にするのに非
常に有効であること、およびそれによつて耐燃性
にされたポリフエニレンエーテル組成物が変色し
ないことが明らかである。同時に耐燃性組成物の
他の性質が難燃剤組成物によつて悪影響を受け
ず、ある場合には衝撃強さの如く改良される。 Table Example 1 PPO® 25 Impact-resistant polystyrene 75 1,2-bis-(tribromophenoxy)-ethane
15.2 Tri-(2-phenylcyclohexyl)-borate
3.0 Ferrocene 0.7 Properties UL94 Test SE Heating Deflection Temperature, 〓/264psi2″ Span 195 Color Original Very Bright Notched Izotz Impact Strength 2.8 Tensile Yield Strength 6600 Ultimate Tensile Strength 6100 Elongation, % 53 From the above results It is clear that the flame retardant composition according to the invention is very effective in making polyphenylene ether compositions flame resistant and that the polyphenylene ether compositions rendered flame resistant thereby do not discolor. At the same time, other properties of the flame resistant composition are not adversely affected by the flame retardant composition and in some cases are improved, such as impact strength.
上述した特許および／または特許出願は引用し
てここに組入れる。上記教示より見て本発明の他
の改変が可能であることは明らかである。例えば
ポリ（２，６−ジメチル−１，４−フエニレンエ
ーテル）の代りにポリ（２，６−ジメチル−コ−
２，３，６−トリメチル−１，４−フエニレンエ
ーテル）の如き共重合体を使用できる。また組成
物は充填剤および／または強化剤を含有しうる。
従つて特許請求の範囲に規定した本発明の目的と
する範囲内で本発明の具体例において改変をなし
うることは理解すべきである。 The patents and/or patent applications mentioned above are incorporated herein by reference. Obviously, other modifications of the present invention are possible in light of the above teachings. For example, instead of poly(2,6-dimethyl-1,4-phenylene ether),
Copolymers such as 2,3,6-trimethyl-1,4-phenylene ether) can be used. The composition may also contain fillers and/or reinforcing agents.
Therefore, it should be understood that modifications may be made to the embodiments of the invention without departing from the scope of the invention as defined in the claims.
Claims (1)
および (b) 250〜300℃で安定である難燃剤５〜10重量部 (c) 消炎増強剤 を含有し、上記難燃剤が、 (i) 硼素含有エステル、および (ii) 臭素化フエノキシアルカン からなり、上記難燃剤中の(b)(i)および(b)(ii)の割合
が、(b)(i)１〜３重量部および(b)(ii)10〜25重量部で
ある難燃性ポリフエニレンエーテル樹脂組成物。 ２ ポリフエニレンエーテルが式 （式中、Ｑ、Q′、Q″およびＱはそれぞれ独立
に、水素、炭化水素基、ハロゲン原子とフエニル
核の間に少なくとも二つの炭素原子を有するハロ
炭化水素基、炭化水素オキシ基およびハロゲン原
子とフエニル核の間に少なくとも二つの炭素原子
を有するハロ炭化水素オキシ基からなる群から選
択し、Q′、Q″およびＱは更にハロゲンである
ことができる、ただしＱおよびQ′は三級炭素原
子を含有しないのが好ましい、ｎは単量体残基の
合計数を表わし、少なくとも50の整数である）の
ものである特許請求の範囲第１項記載の耐燃性ポ
リフエニレンエーテル樹脂組成物。 ３ ポリフエニレンエーテル成分がポリ（２，６
−ジアルキル−１，４−フエニレン）エーテルで
ある特許請求の範囲第１項記載の耐燃性ポリフエ
ニレンエーテル樹脂組成物。 ４ ポリフエニレンエーテル成分がポリ（２，６
−ジメチル−１，４−フエニレン）エーテルであ
る特許請求の範囲第１項記載の耐燃性ポリフエニ
レンエーテル樹脂組成物。 ５ 難燃剤が１，２−ビス−（トリブロモフエノ
キシ）−エタンおよびトリ−（２−フエニルシクロ
ヘキシル）−ボレートの組合せを含有する特許請
求の範囲第１項記載の耐燃性ポリフエニレンエー
テル樹脂組成物。 ６ ポリフエニレンエーテル樹脂がポリスチレン
とのブレンドである特許請求の範囲第１項記載の
耐燃性ポリフエニレンエーテル樹脂組成物。 ７ 消炎増強剤がフエロセンである特許請求の範
囲第１項記載の耐燃性ポリフエニレンエーテル樹
脂組成物。 ８ 充填剤および／または強化材を含有する特許
請求の範囲第１項記載の耐燃性ポリフエニレンエ
ーテル樹脂組成物。[Claims] 1. For 100 parts by weight of the composition: (a) 75 to 90 parts by weight of polyphenylene ether resin;
and (b) 5 to 10 parts by weight of a flame retardant that is stable at 250 to 300°C (c) a flame retardant, the flame retardant comprising: (i) a boron-containing ester; and (ii) a brominated phenoxy. The proportion of (b)(i) and (b)(ii) in the flame retardant is 1 to 3 parts by weight for (b)(i) and 10 to 25 parts by weight for (b)(ii). A flame retardant polyphenylene ether resin composition. 2 Polyphenylene ether is the formula (In the formula, Q, Q', Q'' and Q each independently represent hydrogen, a hydrocarbon group, a halohydrocarbon group having at least two carbon atoms between a halogen atom and a phenyl nucleus, a hydrocarbonoxy group, and a halogen selected from the group consisting of halohydrocarbonoxy groups having at least two carbon atoms between the atom and the phenyl nucleus, Q', Q'' and Q can further be halogen, provided that Q and Q' are tertiary The flame-resistant polyphenylene ether resin composition according to claim 1, preferably containing no carbon atoms, where n represents the total number of monomer residues and is an integer of at least 50. thing. 3 The polyphenylene ether component is poly(2,6
2. The flame-resistant polyphenylene ether resin composition according to claim 1, which is a -dialkyl-1,4-phenylene) ether. 4 The polyphenylene ether component is poly(2,6
2. The flame-resistant polyphenylene ether resin composition according to claim 1, which is (dimethyl-1,4-phenylene) ether. 5. The flame-resistant polyphenylene of claim 1, wherein the flame retardant contains a combination of 1,2-bis-(tribromophenoxy)-ethane and tri-(2-phenylcyclohexyl)-borate. Ether resin composition. 6. The flame-resistant polyphenylene ether resin composition according to claim 1, wherein the polyphenylene ether resin is a blend with polystyrene. 7. The flame-resistant polyphenylene ether resin composition according to claim 1, wherein the anti-inflammatory enhancer is ferrocene. 8. The flame-resistant polyphenylene ether resin composition according to claim 1, which contains a filler and/or a reinforcing material.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US34235582A | 1982-01-25 | 1982-01-25 | |
| US342355 | 2003-01-15 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58129030A JPS58129030A (en) | 1983-08-01 |
| JPH0344106B2 true JPH0344106B2 (en) | 1991-07-04 |
Family
ID=23341481
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP925683A Granted JPS58129030A (en) | 1982-01-25 | 1983-01-21 | Coloration-preventive flame retardant comprising stabilized halogenated organic cpd and boron cpd |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0085834B1 (en) |
| JP (1) | JPS58129030A (en) |
| DE (1) | DE3371212D1 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63264652A (en) * | 1987-04-21 | 1988-11-01 | Kyodo Yakuhin Kk | Heat stabilization of styrene resin composition containing bromine-containing flame retardant |
| EP0364729A1 (en) * | 1988-10-12 | 1990-04-25 | General Electric Company | Polymer-based material which comprises a flame-retardant and optionally a plasticizer and further conventionally used additives |
| KR0163032B1 (en) * | 1989-03-31 | 1999-01-15 | 오노 알버어스 | Flame retardant compositions |
| NL8901093A (en) * | 1989-05-01 | 1990-12-03 | Gen Electric | MATERIAL CONTAINING AT LEAST 20% POLYPHENYLENE ETHER AND WHICH CONTAIN A SMALL AMOUNT OF FIRE-RETARDANT AND, IF DESIRED, A WEAKER AND FURTHER USUAL ADDITIVES. |
| AT394370B (en) * | 1990-04-24 | 1992-03-25 | Chemie Linz Gmbh | USE OF SPIROCYCLIC boric acid esters as flame retardants in plastics, flame retardant plastics as well as spirocyclic boric acid esters |
| DE4105924A1 (en) * | 1991-02-26 | 1992-08-27 | Basf Ag | LOW SMOKE GAS THERMOPLASTIC MOLDS |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49129750A (en) * | 1973-04-14 | 1974-12-12 | ||
| JPS5162838A (en) * | 1974-11-29 | 1976-05-31 | Toray Industries | NANNENSEIJUSHISOSEIBUTSUNO SEIZOHOHO |
| JPS5513772A (en) * | 1978-07-14 | 1980-01-30 | Velsicol Chemical Corp | Flame resistant composition of improved polystyrene plastic |
| JPS57153035A (en) * | 1981-02-18 | 1982-09-21 | Basf Ag | Self-extinguishing thermoplastic forming material |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3919356A (en) * | 1968-12-09 | 1975-11-11 | Borg Warner | Halogenated norbornene-methanonaphthalene derivatives and their applications |
| DE2063051A1 (en) * | 1970-12-22 | 1972-07-13 | Bayer | Flame retardant rubber hair |
| BE795744A (en) * | 1972-02-23 | 1973-06-18 | Velsicol Chemical Corp | FLAMMATION-DELAYING COMPOSITIONS |
| DE2316204B2 (en) * | 1973-03-31 | 1981-04-16 | Dynamit Nobel Ag, 5210 Troisdorf | Process for the production of 1,2-1,3- or 1,4 - bis (bromomethyl) - tetrachlorobenzenes and their use as flame retardants |
| US3897387A (en) * | 1973-05-23 | 1975-07-29 | Shaughnessy James D O | Fire retardant agent |
| US4144288A (en) * | 1978-01-20 | 1979-03-13 | Pennwalt Corporation | Sodium tetraborate pentahydrate as a smoke suppressant for styrenic resins |
-
1983
- 1983-01-12 EP EP83100202A patent/EP0085834B1/en not_active Expired
- 1983-01-12 DE DE8383100202T patent/DE3371212D1/en not_active Expired
- 1983-01-21 JP JP925683A patent/JPS58129030A/en active Granted
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49129750A (en) * | 1973-04-14 | 1974-12-12 | ||
| JPS5162838A (en) * | 1974-11-29 | 1976-05-31 | Toray Industries | NANNENSEIJUSHISOSEIBUTSUNO SEIZOHOHO |
| JPS5513772A (en) * | 1978-07-14 | 1980-01-30 | Velsicol Chemical Corp | Flame resistant composition of improved polystyrene plastic |
| JPS57153035A (en) * | 1981-02-18 | 1982-09-21 | Basf Ag | Self-extinguishing thermoplastic forming material |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0085834B1 (en) | 1987-04-29 |
| EP0085834A1 (en) | 1983-08-17 |
| DE3371212D1 (en) | 1987-06-04 |
| JPS58129030A (en) | 1983-08-01 |
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